Method of attracting and destroying tobacco beetles with alkyl phenethylethers

ABSTRACT

Described are the compounds, alkyl and alkenyl phenethylether derivatives, defined according to the structure: ##STR1## wherein R represents C 3  or C 6  secondary alkyl (2 o  -alkyl) or C 4  alkenyl which have, individually or in combination, been found to be useful in augmenting or enhancing the aroma of perfumes and perfumed articles as well as colognes and, in addition, in combatting tobacco beetles of the species Lasioderma serricorne (F.).

BACKGROUND OF THE INVENTION

This invention relates to phenethyl alkyl and alkenyl ethers and to theuses thereof in combatting insects as a result of the discovery that thealkyl and alkenyl phenylethers are tobacco beetle pheromones orectohormones; and in addition to the uses of phenethyl alkyl or alkenylethers in augmenting or enhancing the aromas of perfumes, colognes andperfumed articles (e.g., solid or liquid anionic, cationic, nonionic andzwitterionic detergents, fabric softeners, fabric softener articles,hair conditions, odorants and deodorants). Obviously then, the inventionalso relates to one or more pleasant smelling pheromones or ectohormonesuseful for combatting insects yet, at the same time, not repulsive tothe individual or group of individuals applying the pheromone orectohormone to the area where the insects are to be combatted.

Pheromones or ectohormones are secreted by insects as so called sociallyactive ingredients, e.g., as sexual attractants or aggregationsubstances. The use of these pheromones or ectohormones is known toattract insects into certain small sections of a contaminated area, toconcentrate them in this are and then to destroy the insects in anyknown way, e.g., mechanically, chemically or with insecticides. Thismethod leads to a very economical and concentrated use of the actualinsecticides, especially of insecticides which are ecologicallydangerous, whereby the spraying of large parts of the contaiminated areain an expensive way, e.g., by spraying insecticides with an aeroplane,is avoided.

No pheromones have been discovered up to the present time for use withLasioderma serricorne (F.) with the exception of cyclohexylphenethylethers as described in co-pending application for U.S. LettersPatent, Ser. No. 192,238 now U.S. Pat. No. 4,306,096. Thus, thepheromones known up to the present time with the exception of thecyclohexyl phenethylethers of application for U.S. Letters Patent, Ser.No. 192,238 belong to a large variety of chemical substances and are, asa rule, effective only with respect to certain insects such as, forexample, for use in combatting insects of the order coleoptera and thefamily scolytidae and platypodidae which beetles cause substantialdamage to forests and to the wood of trees generally as taught in U.S.Pat. No. 3,927,207 issued on Dec. 16, 1975.

Another problem as yet unsolved by the prior art with the exception ofthe use of cyclohexyl phenethylethers as described in application forU.S. Letters Patent, Ser. No. 192,238 concerns the utilization, eitherin conjunction with or as pheromones or ectohormones for insectattractants, of fragrance imparting, augmenting or enhancing agents.Such fragrance imparting, augmenting or enhancing agents must be eitheridentical to or, at the very least, compatible with the pheromones orectohormones. Previously such pheromones or ectohormones having theirown aroma profiles have been found to have an aroma profile which eitherwas esthetically displeasing or, at the very best, incapable of coveringor deodorizing the chemical-like sharp, abrasive aroma of theinsecticides used against the insects; that is, prior to the finding ofthe cyclohexyl phenethylethers of application for U.S. Letters Patent,Ser. No. 192,238, filed on Sept. 30, 1980.

An optimal solution to the foregoing problems would be to create, in onechemical, a pheromone or ectohormone; an insecticide; and an aromaaugmenting or enhancing substance which is compatible with saidpheromone or ectohormone and with said insecticide.

Notwithstanding the aforementioned pheromone or ectohormone propertiesand notwithstanding the aforementioned insecticide properties, chemicalcompounds which can provide green, fruity, floral, hyacinth-like, rosy,rose-hyacinth-like, galbanum-like cassis-like and narcissus-like aromaswith hyacinth/honey aroma on dry-out and with peppery and mushroomundertones which are both rich and full-bodied as well as long-lastingare desirable in the art of perfumery. Many of the natural materialswhich provide such fragrances and contribute such desired nuances toperfumery compositions are high in cost, unattainable at times, vary inquality from one batch to another and/or are generally subject to theusual variations of natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the fragrance notes provided bynatural essential oils or compositions thereof. Unfortunately, many ofthese synthetic materials either have the desired nuances only to arelatively small degree or else contribute undesirable or unwanted odorto the compositions. The search for materials which can provide morerefined, more natural-like, more long-lasting green, fruity, floral,hyacinth-like, rosy, rose-hyacinth-like, galbanum, cassis-like andnarcissus-like aromas with hyacinth/honey aromas on dry-out and pepperyand mushroom undertones has been difficult and relatively costly in theareas of both natural products and synthetic products.

Arctander in "Perfume and Flavor Chemicals (Aroma Chemicals)", VolumeII, 1969 describes phenylethyl alcohol as having a rose aroma.

The use in perfumery of alkyl ethers of phenylethyl alcohol is known.Thus, Chem. Abstracts, Volume 79, 1973, 18356m abstracts U.S. Pat. No.3,734,970 which discloses the use of phenylethyl alcohol methyletherhaving the structure: ##STR2## in perfumery. It is further indicatedthat this material is produced by reaction of phenylethyl alcohol with amercury-aluminum couple to form triphenylethyoxy aluminum and reactingthe triphenylethoxy aluminum with dimethoxysulfoxide to form thephenylethyl alcohol methylether.

Chem. Abstracts, Volume 87, 1977 87:135063q discloses the genus ofcompounds having the structure: ##STR3## which abstracts Japanese KokaiNo. 77-07,911 and uses of these compounds in perfumery wherein Rrepresents alkyl, alkenyl, alkynyl, aryl, aralkyl and cycloalkyl and R¹represents hydrogen or R and R² represents alkyl or pheylalkyl.

Chem Abstracts 90:127414, Volume 90 (1979) abstracts French Demande2,373,276 which discloses the use of the compound having the structure:##STR4## synthesized according to the reaction sequence: ##STR5## inperfumery particularly as a lilac perfumant.

Nothing in the prior art, however, discloses the specific compoundshaving the structure defined according to the genus: ##STR6## Wherein Ris C₃ or C₆ 2°-alkyl or C₄ alkenyl.

Phenylethyl alcohol isoamylether has been used for several years in theperfumery industry but has been found to have an undesirable "chocolate"nuance. Phenylethyl alcohol isoamylether has the structure: ##STR7## andis a "primary" alkyl ether rather than a "secondary" alkyl ether.

Isobutyl phenylacetate (otherwise known as "Anther") having thestructure: ##STR8## an ester, is described by Arctander "Perfume andFlavor Chemicals" (Aroma Chemicals)) 1969 as being extensively useful inperfumery for fresh "petal" notes in rose, peony, narcisse, carnation,sweet pea, freesia and hyacinth. Arctander also indicates that thismaterial is on a "GRAS" list as having number 2210.

Arctander also indicates at monograph number 514 that isobutylphenylether having the structure: ##STR9## has a harsh chemical odor,sweet but with a metallic chemical background and being remotelyreminiscent of anise.

Phenethyl propionate has been disclosed in the Journal of EconomicEntomology, 66, (5), 1973, and has been indicated by McGovern et al. tobe an attractant for Popillia japonica Newman (Japanese beetles)particularly in combination with eugenol. Indeed, in that same paper byMcGovern et al., it is indicated that trans-2-hexenal, a well-knownperfume ingredient, is also a Japanese beetle attractant. The phenethylpropionate has the structure: ##STR10##

In another paper by McGovern et al, Journal of Economic Entomology,Volume 63, Number 1, page 276, it is indicated that methylcyclohexanepropionate and certain related chemicals are also attractantsfor Popillia japonica Newman.

Research concerning Lasioderma serricorne (F.) and attractants thereforare limited to the use of extracts of natural food odors. Thus, thepaper by Fletcher and Garrett entitled "Ovipositional Response of ThreeStrains of the Cigarette Beetle of Extracts of Food Odors" in TobaccoInternational, 182 (5), pages 166-169, Mar. 7, 1980. Fletcher andGarrett disclose that the ovipositional response of three strains of thecigarette beetle is a function of different food odor attractants.

Nothing in the prior art, however, discloses the unexpected, unobviousand advantageous properties of the phenethylether derivatives having thegeneric structure: ##STR11## wherein R represents C₃ or C₆ 2°-alkyl orC₄ alkenyl which are not only useful per se for augmenting or enhancingthe aroma of perfume compositions, colognes and perfumed articles, butare also useful individually or taken in combination as Lasiodermaserricorne (F.) pheromones and, in addition, as Lasioderma serricorne(F.) insecticides.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product producedaccording to Example IA containing the compound having the structure:##STR12##

FIG. 2 is the NMR spectrum for the reaction product of Example IAcontaining the compound having the structure: ##STR13##

FIG. 3 is the infra-red spectrum for the reaction product of Example IAcontaining the compound having the structure: ##STR14##

FIG. 4 is the GLC profile for the crude reaction product of Example IBcontaining the compound having the structure: ##STR15##

FIG. 5 is the GLC profile for the crude reaction product of Example IIprior to propionic anhydride reaction containing the compounds havingthe structures: ##STR16##

FIG. 6 is the GLC profile for fraction 4 of the distillation product ofthe reaction product of Example II after reaction with propionicanhydride, containing the compound having the structure: ##STR17##

FIG. 7 is the NMR spectrum for the reaction product of Example II afterdistillation containing the compound having the structure: ##STR18##

FIG. 8 is the infra-red spectrum for the reaction product of Example IIafter distillation after reaction with propionic anhydride containingthe compound having the structure: ##STR19##

FIG. 9 is the GLC profile of the reaction product of Example IIIcontaining the compounds having the structures: ##STR20##

FIG. 10A represents the NMR sepctrum for peak 4 of the GLC profile ofFIG. 9 containing the compound having the structure: ##STR21##

FIG. 10B is the infra-red spectrum for peak 4 of FIG. 9 which is the GLCprofile for the reaction product of Example III, containing the compoundhaving the structure: ##STR22##

FIG. 11A is the NMR spectrum for peak 5 of FIG. 9 which is the GLCprofile for the reaction product of Example III, containing thecompounds having the structures: ##STR23##

FIG. 11B is the infra-red spectrum for peak 5 of FIG. 9 which is the GLCprofile of Example III, containing the compounds having the structures:##STR24##

DETAILED DESCRIPTION OF THE DRAWINGS, FIGS. 5 and 9

FIG. 5 is the GLC profile for the crude reaction product of isopropanoland phenylethyl alcohol having the structure: ##STR25## which containsthe compounds phenylethyl alcohol isopropyl ether having the structure:##STR26## and phenylethyl alcohol having the structure: ##STR27##

The peak indicated by the reference numeral "1" represents phenylethylalcohol having the structure: ##STR28##

The peak indicated by the reference numeral "2" represents thephenylethyl alcohol isopropyl ether having the structure: ##STR29##

These two compounds are virtually impossible to separate by distillationand require reaction with propionic anhydride followed by separation ofthe resultant phenylethyl alcohol isopropyl ether and phenylethylalcohol propionate having the structure: ##STR30##

FIG. 9 is the GLC profile for the reaction product of Example III. Thereaction product of Example III contains four compounds:

phenylethyl alcohol having the structure: ##STR31##

2-butenol phenylethylether, cis-isomer and trans-isomer having thestructures: ##STR32##

phenylethyl methallylether having the structure: ##STR33##

The peak on the GLC profile indicated by the reference numeral "3" isthe peak for phenylethyl alcohol having the structure: ##STR34##

The peak on the GLC profile of FIG. 9 indicated by the reference numeral"4" is the peak for the phenylethylether of methallyl alcohol having thestructure: ##STR35##

The peak on FIG. 9, the GLC profile, indicated by the reference numeral"5" is the peak for the phenylethylether of 2-butenol, both the "cis"and "trans" isomers having the structures: ##STR36##

THE INVENTION

The present invention proposes the use of certain phenethylethers whichare alkyl phenethylethers or alkenyl phenethylethers defined accordingto the generic structure: ##STR37## wherein R represents C₃ or C₆2°-alkyl or C₄ alkenyl for combatting beetles of the order Lasiodermaserricorne (F.) in such a manner that one or a combination of the alkylor alkenyl phenethylethers not only acts as a pheromone or ectohormonebut also acts as an aroma augmenting or enhancing agent and, inaddition, acts as an insecticide. Notwithstanding the pheromone andinsecticide properties of the alkyl and alkenyl phenethylethers, theinstant invention also provides alkyl and alkenyl ethers as fragrancescapable of augmenting or enhancing the fragrances of perfumecompositions, colognes and perfumed articles (e.g., solid or liquidanionic, cationic, nonionic or zwitterionic detergents, fabricsofteners, dryer-added fabric softener articles, hair conditioners,deodorants and cosmetic powders).

The alkyl and alkenyl phenethylethers of our invention are capable ofaugmenting or enhancing the green, fruity, floral, hyacinth-like, rosy,rose-hyacinth-like, galbanum-like, cassis-like and narcissus-like aromasof perfumes, perfumed articles and colognes of our invention. Of course,as part of the perfumed articles of our invention is the "perfumedinsecticide-pheromone" compositions of our invention.

The destruction of the Lasioderma serricorne (F.) insects can beachieved by distributing one or a combination of the alkyl and/oralkenyl phenethylethers (which act as pheromonal attractants) in thecontaminated area at separate individual places, namely, by means ofcatch trees. These are impregnated with the attractants which may, ifdesired, act as an insecticide too; or the alkyl and/or alkenylphenethylethers may be augmented by additional insecticides whereuponthe catch trees are sprayed with another insecticide either before orafter the insects have gathered at the catch tree (whatever insects arestill alive after contact with the alkyl and/or alkenylphenethylethers). Instead of using the alkyl and/or alkenylphenethylethers alone or taken together with another insecticide, onemay also use a chemical sterilizing compound. Further, the catch treemay be treated with other chemicals or can be burned. Another possiblemethod for destroying insects with the alkyl and/or alkenylphenethylethers according to our invention makes use of the disturbanceor perturbance theory. Instead of physically destroying the insects witheither high concentrations of the alkyl and/or alkenyl phenethylethersor by using the alkyl and/or alkenyl phenethylethers followed by anadditional insecticide, it is also possible to combine the alkyl and/oralkenyl phenethylethers physically with another stronger insecticidebefore using. Thus, it is possible now to spray a combination of alkyland/or alkenyl phenethylethers which have pleasant aromas in combinationwith insecticides whose original aroma(s) is covered using the alkyland/or alkenyl phenethylethers in certain centrally located areas or inthe form of rows in the contaminated area. Furthermore, the alkyl and/oralkenyl phenethylethers can be mixed with the usual solid or liquidcarriers or with biocides such as stronger insecticides, pesticides orherbicides. The mixture may contain surface active agents to obtain abetter distribution or adherence to the plants.

The alkyl and/or alkenyl phenethylethers of our invention may beprepared by reacting β-phenylethyl alcohol with an appropriate C₃ or C₆lower secondary alkanol or a C₄ alkenol in the presence of an acid suchas sulfuric acid according to the reaction. ##STR38## Alternatively,sodium phenethyl alcoholate may be reacted with a C₃ or C₆ secondaryalkyl chloride or a C₄ alkenyl chloride or a sodium alkyl alcoholate ora sodium alkenyl alcoholate may be reacted with β-phenylethyl chlorideor β-phenylethyl bromide by means of a "Williamson" synthesis,conventional in the organic chemistry art.

A novel aspect of our invention lies in the preparation of the isopropylphenethylether of our invention having the structure: ##STR39## Whenisopropyl alcohol is reacted with phenylethyl alcohol, not all of thephenylethyl alcohol will react and thus, a mixture of phenylethylalcohol having the structure: ##STR40## and isopropyl phenethyletherhaving the structure: ##STR41## is formed.

Another aspect of our invention involves the production of the isopropylphenethylether. In reacting the phenylethyl alcohol having thestructure: ##STR42## with the isopropanol in the presence of an acidcatalyst, for example, sulfuric acid, a mixture of two compounds isformed: the isopropyl phenethylether and unreacted phenylethyl alcohol.It is impossible to separate this mixture whereby the isopropylphenethylether is produced in pure form and, accordingly, we have foundthat the mixture of isopropyl phenethylether and phenylethyl alcohol maybe easily reacted with propionic anhydride to form a mixture ofisopropyl phenethylether having the structure: ##STR43## and thephenylethyl alcohol propionate having the structure: ##STR44## Theresulting mixture of isopropyl phenethylether and phenylethyl alcoholpropionate may then be easily separated by fractional separation toyield substantially pure isopropyl phenethylether in high yields. Informing the mixture of isopropyl phenethylether and phenylethyl alcoholpropionate from the mixture of isopropyl phenethylether and phenylethylalcohol with propionic anhydride, it is preferred to carry out thereaction at reflux conditions in the presence of an easily separatablesolvent which is inert to the reaction mass such as toluene. Theforegoing reaction sequence is illustrated as follows: ##STR45## and ismore specifically illustrated in Example II, infra.

Notwithstanding the pheromonal and insecticidal activity of the alkyland/or alkenyl phenethylethers of our invention, the alkyl and/oralkenyl phenethylethers of our invention can be used to contribute longlasting green, fruity, floral, hyacinth-like, rosy, rose-hyacinth-like,galbanum-like, cassis-like and narcissus-like aromas with hyacinth/honeyaromas on dry-out and with peppery and mushroomy undertones which areunexpectedly full and rich for very long periods of time, to perfumes,perfumed articles and colognes.

As olfactory agents, the alkyl and/or alkenyl phenethylethers of ourinvention can be formulated into or used as components of a "perfumecomposition" or can be used as components of a "perfumed article" or theperfume composition may be added to "perfumed articles".

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, alcohols, aldehydes, ketones,nitriles, ethers in addition to and other than the alkyl and alkenylphenethylethers of our invention, lactones, natural essential oils,synthetic essential oils and frequently hydrocarbons which are admixedso that the combined odors of the individual components product apleasant or desired fragrance. Such perfume compositions usually contain(a) the main note or the "bouquet" of foundation stone of thecomposition; (b) modifiers which round off and accompany the main note;(c) fixatures which include odorous substances which lend a particularnote to the perfume throughout all stages of evaporation, and substanceswhich retard evaporation; and (d) top notes which are usuallylow-boiling, fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, the alkyl and/or alkenyl phenethylethers of ourinvention can be used to alter the aroma characteristics of a perfumecomposition, for example, by highlighting or moderating the olfactoryreaction contributed by another ingredient in the composition.Furthermore, the alkyl and/or alkenyl phenethylethers of our inventioncan be used in combination with the cyclohexyl phenethylether as claimedin earlier filed application for U.S. Letters Patent Ser. No. 192,238filed on Sept. 30, 1980. The disclosure of said application for U.S.Letters Patent, Ser. No. 192,238 filed on Sept. 30, 1980 is herebyincorporated by reference in the instant specification. The amount ofalkyl and/or alkenyl phenethylethers that may be used in conjunctionwith the cyclohexyl phenethylether of Ser. No. 192,238 filed on Sept.30, 1980 may vary from about 1:99 up to about 99:1 whereby veryinteresting hyacinth-like, rosy, rose-hyacinth-like, galbanum-likearomas with cassis-like, narcissus-like peppery and mushroomy undertonesare achieved.

The amount of alkyl and/or alkenyl phenethylether of our invention whichwill be effective in perfume compositions depends upon many factors,including the other ingredients, their amounts and the effects which aredesired. It has been found that perfume compositions containing aslittle as 0.05% of the alkyl and/or alkenyl phenethylether of ourinvention taken alone or in combination with the cyclohexylphenethylether, or even less can be used to impart long lasting,interesting, very strong, green, fruity, floral, hyacinth-like, rosy,rose-hyacinth-like, galbanum-like, cassis-like and narcissus aromas tosoaps, liquid and solid cationic, nonionic, anionic and zwitterionicdetergents, cosmetic powders, liquid and solid fabric softeners,dryer-added fabric softener articles, optical brightener compositionsand other products. The amount employed can range up to 50% or more andwill depend upon considerations of cost, nature of the end product andthe effect desired on the finished product and particular fragrancesought.

The alkyl and/or alkenyl phenethylethers of our invention can be usedalone or in a perfume composition as an olfactory component indetergents and soaps, space odorants and deodorants, perfumes; colognes,toilet waters; bath salts; hair preparations such as lacquers,brilliantines, pomades and shampoos; cosmetic preparations such ascreams, deodorants, hand lotions and sun screens; powders such as talcs,dusting powders, face powder and the like. When used as an olfactorycomponent of a perfumed article, as little as 0.01% of the alkyl and/oralkenyl phenethylether taken alone or in combination with cyclohexylphenethylether will suffice to impart an interesting, long-lastinggreen, fruity, floral, hyacinth-like, rosy, rose-hyacinth-like,galbanum-like, cassis and narcissus-like aroma. Generally no more than0.5% is required in the perfumed article.

In addition, the perfume composition can contain a vehicle or carrierfor the alkyl and/or alkenyl phenethylether alone or in combination withthe cyclohexyl phenethylether or in combination with still otheringredients. The vehicle can be a liquid such as an alcohol such asethanol, a glycol such as propylene glycol or the like. The carrier canbe an absorbent solid such a gum or components for encapsulating thecomposition such as gelatin which can be used to form a capsule wallsurrounding the perfume oil by means of coacervation.

It will thus be apparent that the alkyl and/or alkenyl phenethylethersof our invention can be used to alter, modify, augment or enhance thearoma of a wide variety of consumable materials including fragranceformulations, colognes, pheromones and perfumed articles in general.

The following examples serve to illustrate our invention and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE IA Preparation of 4-Methyl-2-Pentanyl Phenethylether ##STR46##

Into a 3 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle is placed 732 grams of phenylethylalcohol, 1052 grams of 4-methyl-2-pentanol and 100 grams of concentrated(93%) sulfuric acid. The reaction mass is heated to reflux and water iscontinuously taken off through a Bidwell trap. The reaction mass isrefluxed for a period of 14 hours.

At the end of the reaction, the reaction mass is quenched with 3 litersof water, washed with aqueous sodium carbonate (saturated) and then withsaturated sodium chloride (aqueous).

The reaction mass is then brushed over followed by fractionaldistillation to yield the following fractions:

    ______________________________________                                                Vapor   Liquid   Head          Weight                                 Fraction                                                                              Temp.   Temp.    Vac.   Reflux of                                     Number  (°C.)                                                                          (°C.)                                                                           mm/Hg. Ratio  Fraction                               ______________________________________                                        1       40       80      4      9:1    52.7                                   2       64       86      2      9:1    48.7                                   3       68       90      2      9:1    29.1                                   4       68       92      2      9:1    27.7                                   5       68       93      2      9:1    18.7                                   6       70       99      1.8    9:1    27.4                                   7       78      100      3      2:1    27.0                                   8       80      105      2      2:1    24.8                                   9       80      105      2      2:1    27.9                                   10      80      105      2      2:1    22.4                                   11      80      105      2      2:1    28.2                                   12      80      105      2      2:1    25.5                                   13      80      108      2      2:1    27.2                                   14      87      114      2      2:1    19.5                                   15      99      172      2      2:1    26.5                                   16      93      220      3.5    2:1    14.5                                   ______________________________________                                    

FIG. 1 is the GLC profile for the crude reaction product producedaccording to Example IA containing the compound having the structure:##STR47##

FIG. 2 is the NMR spectrum for the reaction product of Example IAcontaining the compound having the structure: ##STR48##

FIG. 3 is the infra-red spectrum for the reaction product of Example IAcontaining the compound having the structure: ##STR49##

EXAMPLE IB Preparation of 4-Methyl-2-Pentanyl Phenethylether ##STR50##

Into a 10 liter reaction vessel equipped with stirrer, therometer,reflux condenser and heating mantle is placed 1428 grams of4-methyl-2-pentanol; 915 grams of phenylethyl alcohol and 500 grams ofsulfuric acid. The reaction mass is heated to reflux (105° C.) andrefluxed for a period of 2 hours.

FIG. 4 is the GLC profile for the crude reaction mass.

EXAMPLE II Preparation of Isopropyl Phenethylether ##STR51##

Into a 10 liter reaction flask is placed 1440 grams of isopropyl alcoholand 732 grams of phenylethyl alcohol. Over a period of 1 hour, asolution of 270 grams of sulfuric acid and 30 ml water is added slowly.At the end of the addition of the sulfuric acid solution, the reactionmass is heated to reflux and the reaction mass is refluxed for a periodof 4 hours. At the end of the 4 hour period, three liters of water isadded to the reaction mass and the reaction mass is neutralized with 50%sodium hydroxide. One liter of toluene is added and the toluene layer isseparated from the aqueous layer.

To the toluene mixture is added 260 grams of propionic anhydride and thepropionic anhydride/toluene/phenylethyl alcohol/isopropyl phenethylethermixture is then refluxed for a period of 30 minutes. The reaction massis then cooled down and one liter of water is added thereto. Thereaction mass is then washed with 50% caustic followed by saturatedsodium chloride and then neutralized with saturated sodium bicarbonate.

The reaction mass is then distilled yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Head   Weight                                     Fraction  Temp.   Temp.     Vac.   of                                         Number    (°C.)                                                                          (°C.)                                                                            mm/Hg. Fraction                                   ______________________________________                                        1         24/70   24/101    1.8/1.8                                                                               4.2                                       2         70      101       1.4    12.4                                       3         60      101       1.1    14.5                                       4         65      102       1.1    21.0                                       5         65      104       1.0    27.8                                       6         60       86       1.0    22.3                                       7         58      110       1.3    26.3                                       8         59      112       1.3    26.8                                       9         64      113       1.3    23.9                                       10        65      113       1.4    25.8                                       11        70      115       1.3    28.2                                       12        72      115       1.3    29.2                                       13        74      115       1.3    29.6                                       14        76      116       1.3    30.0                                       15        77      116       1.3    29.3                                       16        76      115       1.2    29.1                                       17        76      115       1.2    27.7                                       18        76      115       1.2    28.9                                       19        77      116       1.2    28.9                                       20        77      116       1.2    29.5                                       21        78      117       1.2    27.8                                       22        79      117       1.2    29.6                                       23        79      117       1.2    25.0                                       24        82      126       1.2    25.0                                       25        83      128       1.2    27.1                                       26        85      156       1.2    29.2                                       27        106     250       1.2    18.9                                       ______________________________________                                    

FIG. 5 is the GLC profile for the crude reaction product of Example IIprior to propionic anhydride reaction containing the compounds havingthe structures: ##STR52##

FIG. 6 is the GLC profile for fraction 4 of the distillation product ofthe reaction product of Example II after reaction with propionicanhydride, containing the compound having the structure: ##STR53##

FIG. 7 is the NMR spectrum for the reaction product of Example II afterdistillation containing the compound having the structure: ##STR54##

FIG. 8 is the infra-red spectrum for the reaction product of Example IIafter distillation after reaction with propionic anhydride containingthe compound having the structure: ##STR55##

EXAMPLE III Preparation of 2-Butenyl Phenethylether and 1-MethallylPhenethylether ##STR56##

Crotyl alcohol (216grams) is slowly added to a stirred slurry ofphenylethyl alcohol (366 grams) and Amberlyst® 15 (cation exchange resinmanufactured by the Rohm & Haas Company, Philadelphia, Pennsylvania; anacid cation exchange resin which is sulfonated polystyrene) at 100° C.The reaction mass is aged at 100° C. for a period of 5 hours whereuponthe solution is cooled and filtered. The organic solution is washed with25% aqueous sodium hydroxide. The GLC profile of the crude reactionproduct is set forth in FIG. 9 (conditions: 10% SE-30 packed columnprogrammed at 120°-220° C. at 8° C. per minute). Peak 3 is the peak forphenylethyl alcohol; peak 4 is the peak for the 1-methallylphenethylether; peak 5 is the peak for 2-butenyl phenethylether (cis andtrans isomers).

A portion of the product is isolated by GLC preparative chromatography.

FIG. 10A represents the NMR spectrum for peak 4 of the GLC profile ofFIG. 9 containing the compound having the structure: ##STR57##

FIG. 10B is the infra-red spectrum for peak 4 of FIG. 9 which is the GLCprofile for the reaction product of Example III, containing the compoundhaving the structure: ##STR58##

FIG. 11A is the NMR spectrum for peak 5 of FIG. 9 which is the GLCprofile for the reaction product of Example III, containing thecompounds having the structures: ##STR59##

FIG. 11B is the infra-red spectrum for peak 5 of FIG. 9 which is the GLCprofile of Example III, containing the compounds having the structures:##STR60##

EXAMPLE IV

Field tests are made each time using 100 male and 100 female Lasiodermaserricorne (F.) cigarette beetles. The beetles were released at acertain distance from the source of attraction which was treated witheither of 1,3-dimethyl butyl phenethylether prepared according toExample IA, isopropyl phenethylether prepared according to Example II orthe mixture of 2-butenyl phenethylether and 1-methallyl phenethyletherprepared according to Example III. Further, felled trees having alreadybeen contaminated with the respective beetles are positioned at bothsides of the starting point. After a certain period of time the amountof insects gathered at the source of attraction was determined thusindicating the effectiveness of the pheromonal mixtures according to theinvention.

Field tests with Lasioderma serricorne (F.) are made whereby thedistance between the starting point and the source of attraction is 50meters. Four independent field tests were made whereby 42% of the malebeetles and 46% of the female beetles gathered at each catch tree. Theconcentration of insects at the catch tree was 58% of the male insectsand 59% of the female insects. In all these tests the catch tree wasimpregnated with 0.7% ethanolic solutions of one of the followingmaterials:

(a) 1,3-dimethyl butyl phenethylether prepared according to Example IA

(b) isopropyl phenethylether prepared according to Example II

(c) a mixture of 2-butenyl phenethylether and 1-methallyl phenethyletherprepared according to Example III

(7 grams of phenethylether derivative per 92 grams of 95% aqueousethanol).

EXAMPLE V

During two consecutive days several felled oak trees surrounding a fieldof tobacco plants were treated with 250 mg of:

(a) 1,3-dimethyl butyl phenethylether prepared according to Example IA

(b) isopropyl phenethylether prepared according to Example II

(c) a mixture of 2-butenyl phenethylether and 1-methallyl phenethyletherprepared according to Example III

in 1.0% ethanolic solution. These trees were exposed in an area whichwere contaminated with Lasioderma serricorne (F.). After 3 to 4 days,115 beetles per square meter were observed on the logs. Other untreatedlogs or trees in the direct neighborhood of the treated logs or treesshowed very few (about 12) insects per square meter on the average whileother trees at a distance of 10 to 20 meters showed no contamination.

EXAMPLE VI

In a large test field, mixtures of either:

(a) 1,3-dimethyl butyl phenethylether prepared according to Example IA

(b) isopropyl phenethylether prepared according to Example II

(c) a mixture of 2-butenyl phenethylether and 1-methallyl phenethyletherprepared according to Example III

in admixture with different DDT preparations, fluorine-containingmixtures and arsen-containing mixtures as well as hexachloro-cyclohexanewere used. These mixtures contained also small amounts of surface-activeagents and carriers. The mixtures were applied to catch trees namelylogs of oak trees in an area of tobacco plants contaminated withLasioderma serricorne (F.). The distance between the catch trees wasalways 200 meters. After 8 days there was no contamination either in thetobacco fields or around the oak trees. About 93% of the Lasiodermaserricorne (F.) insects were destroyed. Surprisingly, it was found thatafter the fourth day the attracting effect was not diminished in spiteof the dead insects being present. Furthermore, in those areas where thephenethylether derivatives of either Examples IA, II or III was usedalone, the average number of insects destroyed was about 78% which initself is surprising. Thus, the phenethylether derivatives of eitherExamples IA, II or III not only act as pheromones but also asinsecticides. Furthermore, the entire area wherein the phenethyletherderivatives of either Example IA, II or III were used had faint,pleasant, floral aromas covering any adverse and estheticallydispleasing aromas of any other insecticides that were used.

EXAMPLE VII

The following mixtures is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Phenylacetic acid      70.0                                                   Coumarin               20.0                                                   Phenylethylphenyl acetate                                                                            100.0                                                  Phenylethyl alcohol    5.0                                                    Benzyl benzoate        100.0                                                  Dimethylphenylethyl carbinol                                                                         10.0                                                   Methyl anthranilate    5.0                                                    Beta ionone            10.0                                                   either:                                                                       (a) 1,3-dimethyl butyl phenethylether                                         prepared according to Example IA; or                                          (b) isopropyl phenethylether prepared                                         according to Example II; or                                                   (c) the mixture of 2-butenyl phen-                                            ethylether and 1-methallyl phen-                                              ethylether prepared according to                                              Example III            30.0                                                   ______________________________________                                    

The 1,3-dimethyl butyl phenethylether prepared according to Example IAimparts the fruity, floral, hyacinth, rose aroma to this honey fragrancewhile giving it a very warm undertone in imparting a very long-lastingrose topnote to this fragrance.

The isopropyl phenethylether prepared according to Example II impartsthe strong green, floral, fruity, hyacinth aroma with a slight peppery,mushroom undertone to this honey fragrance.

The mixture of 2-butenyl phenethylether and 1-methallyl phenethyletherproduced according to Example III imparts the green, floral aroma tothis honey fragrance.

EXAMPLE VIII Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of one of the perfume compositionsprepared according to Example VII. Each of the perfume compositions hasan excellent floral aroma.

EXAMPLE IX Perfumed Liquid Detergent

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApril 6, 1976) with floral aroma nuances are prepared containing 0.10%,0.15%, and 0.20% of each of the fragrances prepared according to ExampleVII. They are prepared by adding and homogeneously admixing theappropriate quantity of one of the three fragrance formulations preparedaccording to Example VII in the liquid detergents. The detergents allpossess excellent floral aromas, the intensity increasing with greaterconcentrations of perfume composition prepared according to Example VII.

EXAMPLE X Preparation of a Cologne and Handkerchief Perfume

The compositions prepared according to Example VII are incorporated intocolognes at concentrations of 2.0%, 2.5%, 3.0%, 4.0%, 4.5% and 5.0% in80%, 85%, 90% and 95% aqueous food grade ethanol; and into handkerchiefperfumes at concentrations of 15%, 20% and 30% (in 80%, 85% and 95%aqueous food grade ethanol). Distinctive and definitive strong, floralaromas are imparted to the colognes and to the handkerchief perfumes atall levels indicated.

EXAMPLE XI Preparation of Soap Composition

100 grams of soap chips are mixed with 1 gram of each of theformulations of Example VII until homogeneous compositions are obtained.The homogeneous compositions are each heated under three atmospherespressure at 180° C. for periods of 3 hours and the resulting liquids areplaced into soap molds. The resulting soap cakes, on cooling, manifestexcellent floral aromas that are very long lasting.

EXAMPLE XII Preparation of a Solid Detergent Composition

A detergent is prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948:

    ______________________________________                                                          Percent by Weight                                           ______________________________________                                        "Neodol 45-11" (a C.sub.14 -C.sub.15                                          alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                                       12                                                        Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent is admixed with 0.15 gram samples of each of the threehoney based perfumes of Example VII. Each of the detergent samples haveexcellent floral, honey-like aromas.

EXAMPLE XIII Dryer-Added Fabric Softener Article

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396, a nonwoven cloth substrate useful as a dryer-added fabricsoftening article of manufacture is prepared wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.);

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of the phenethylether substances as set forth in Table I below

Fabric softening compositions prepared as set forth above having aromaprofiles as set forth in Table I below each consist of a substratehaving a weight of about 3 grams per 100 square inches, a substratecoating of about 1.85 grams per 100 square inches of substrate and anouter coating of about 1.4 grams per 100 square inches of substrate,thereby providing a total aromatized substrate and outer coating weightratio of about 1:1. Aromas are imparted in a pleasant manner to the headspace in the dryer on operation thereof using said dryer-added fabricsoftening nonwoven fabric.

                  TABLE I                                                         ______________________________________                                                        Organoleptic Properties in Head                                               Space above Dryer and of Dryer-                               Phenethylether  Added Fabric Softener Article                                 Derivative      per se                                                        ______________________________________                                        1,3-dimethyl butyl                                                                            A galbanum, cassis-like, rosy,                                phenethylether produced                                                                       hyacinth and narcissus aroma.                                 according to Example I.                                                       Isopropyl phenethylether                                                                      A strong, green, floral, fruity,                              prepared according to                                                                         hyacinth aroma with a slight                                  Example II.     peppery and mushroomy undertone                                               with honey/hyacinth topnotes.                                 Mixture of 2-butenyl                                                                          A green, floral aroma.                                        phenethylether and                                                            1-methallyl phenethylether                                                    produced according to                                                         Example III.                                                                  ______________________________________                                    

EXAMPLE XIV

A liquid detergent composition prepared according to Example IV ofUnited Kingdom Pat. No. 1,498,520 whereby the following ingredients areadmixed:

    ______________________________________                                        Ingredient              Weight %                                              ______________________________________                                        Coconut alcohol ethoxylate                                                                            30                                                    Linear alkyl benzene sulfonate,                                               triethanolamine salt                                                          (alkyl = C.sub.11.8 avg.)                                                                             10                                                    Potassium chloride      3                                                     Triethanolamine         3                                                     Triethanolammonium citrate                                                                            2                                                     Ethyl alcohol           5                                                     Soil release ether "D"  1.0%                                                  Phenethylether derivative as                                                  set forth in Table II below                                                                           3.0                                                   Water                   Balance                                               ______________________________________                                    

The soil release ether "D" is defined according to Table II on page 15of United Kingdom Pat. No. 1,498,520.

This composition is prepared by admixing all of the ingredientsexclusive of soil release after "D" and agitating the mixture until allelectrolytes are dissolved. Soil release ether "D" is then admixed withthe solution in the form of a dry powder which passes through a 150 meshstandard sieve. The resulting composition is in the liquid state and iseasily pourable. The composition is found not to redden on contact withplastic bottles, does not gel with water and has an aroma as set forthin Table II below which lasts for several weeks when exposed to theatmosphere.

                  TABLE II                                                        ______________________________________                                        Phenethylether  Organoleptic Properties of                                    Derivative      Detergent Composition                                         ______________________________________                                        1,3-dimethyl butyl                                                                            A galbanum, cassis-like, rosy,                                phenethylether produced                                                                       hyacinth and narcissus aroma.                                 according to Example I.                                                       Isopropyl phenethylether                                                                      A strong, green, floral, fruity,                              prepared according to                                                                         hyacinth aroma with a slight                                  Example II.     peppery and mushroomy undertone                                               with honey/hyacinth topnotes.                                 Mixture of 2-butenyl                                                                          A green, floral aroma.                                        phenethylether and                                                            1-methallyl phenethylether                                                    produced according to                                                         Example III.                                                                  ______________________________________                                    

The foregoing compositions are added to an aqueous laundrying bath atconcentrations of 0.20% (weight) each at a temperature of 55° C., waterhardness 7 grains per gallon and a pH of 10.0. Polyester and mixedpolyester/cotton fabrics are laundered in the bath for a period of 10minutes after which the fabrics are thoroughly rinsed with fresh waterand dried at ambient temperatures. The fabrics are provided with a soilrelease finish. The head space above the fabrics have pleasant aromas asdescribed in Table II above and are also rather long-lasting (about 3days).

EXAMPLE XV Preparation of Cosmetic Powder Compositions

Cosmetic powders are prepared by admixing in a ball mill, 100 grams oftalcum powder with 0.25 grams of the phenethylether derivative as setforth in Table III below. The resulting cosmetic powders have aromas asset forth in Table III below which are very long-lasting.

                  TABLE III                                                       ______________________________________                                        Phenethylether  Organoleptic Properties of                                    Derivative      Cosmetic Powder                                               ______________________________________                                        1,3-dimethyl butyl                                                                            A galbanum, cassis-like, rosy,                                phenethylether produced                                                                       hyacinth and narcissus aroma.                                 according to Example I.                                                       Isopropyl phenethylether                                                                      A strong, green, floral, fruity,                              prepared according to                                                                         hyacinth aroma with a slight                                  Example II.     peppery and mushroomy undertone                                               with honey/hyacinth topnotes.                                 Mixture of 2-butenyl                                                                          A green, floral aroma.                                        phenethylether and                                                            1-methallyl phenethylether                                                    produced according to                                                         Example III.                                                                  ______________________________________                                    

EXAMPLE XVI Perfumed Liquid Detergent

Concentrated liquid detergents (lysine sale of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with aromas as set forth in Table IV below are preparedcontaining 0.10%, 0.15%, 0.20% and 0.25% of the phenethyletherderivatives as set forth in Table IV below. They are prepared by addingand homogeneously admixing the appropriate quantities of phenethyletherderivatives in the liquid detergent. The detergents all possess intenseand long-lasting aromas as set forth in Table IV below.

                  TABLE IV                                                        ______________________________________                                        Phenethylether                                                                Derivative      Detergent Aroma Profile                                       ______________________________________                                        1,3-dimthyl butyl                                                                             A galbanum, cassis-like, rosy,                                phenethylether produced                                                                       hyacinth and narcissus aroma.                                 according to Example I.                                                       Isopropyl phenethylether                                                                      A strong, green, floral, fruity,                              prepared according to                                                                         hyacinth aroma with a slight                                  Example II.     peppery and mushroomy undertone                                               with honey/hyacinth topnotes.                                 Mixture of 2-butenyl                                                                          A green, floral aroma.                                        phenethylether and                                                            1-methallyl phenethylether                                                    produced according to                                                         Example III.                                                                  ______________________________________                                    

EXAMPLE XVII Preparation of Colognes and Handkerchief Perfumes

Phenethylether derivatives as set forth in Table V below areincorporated into colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%,4.0% and 4.5% in 80%, 85%, 90% and 95% aqueous food grade ethanol; andinto handkerchief perfumes at concentrations of 15%, 20%, 25% and 30%(in 80%, 90% and 95% aqueous ethanol solutions). Distinctive aromas asset forth in Table V below which are very long-lasting on dry-out (44hours) are imparted to the colognes and to the handkerchief perfumes atthe various above levels indicated.

                  TABLE V                                                         ______________________________________                                        Phenethylether Organoleptic Properties of                                     Derivative     Colognes and Handkerchief Perfumes                             ______________________________________                                        1,3-dimethyl butyl                                                                           A galbanum, cassis-like, rosy,                                 phenethylether produced                                                                      hyacinth and narcissus aroma.                                  according to Example I.                                                       Isopropyl phenethylether                                                                     A strong, green, floral, fruity,                               prepared according to                                                                        hyacinth aroma with a slight                                   Example II.    peppery and mushroomy undertone                                               with honey/hyacinth topnotes.                                  Mixture of 2-butenyl                                                                         A green, floral aroma.                                         phenethylether and                                                            1-methylallyl phenethylether                                                  produced according to                                                         Example III.                                                                  ______________________________________                                    

What is claimed is:
 1. A method of attracting and destroying Lasiodermaserricorne (F.) comprising applying to an area contaminated with saidLasioderma serricorne (F.) at least one phenethylether defined accordingto the structure: ##STR61## wherein R is isopropyl or 1,3-dimethylbutye,said attractant being applied to said area in an amount sufficient toattract said Lasioderma serricorne (F.).